CN112823198A

CN112823198A - Upgrading of heavy oil for steam cracking process

Info

Publication number: CN112823198A
Application number: CN201980066342.4A
Authority: CN
Inventors: 崔基玄; 马赞·M·法特希; 穆尼夫·F·阿尔卡尔祖; 班达尔·K·阿勒奥泰比
Original assignee: Saudi Arabian Oil Co
Current assignee: Saudi Arabian Oil Co
Priority date: 2018-10-12
Filing date: 2019-10-11
Publication date: 2021-05-18
Also published as: US20200115644A1; EP3856875A1; JP2022504390A; KR102519057B1; US10526552B1; WO2020077187A1; US20210189264A1; KR20210060606A; US11230675B2; SG11202102756SA; US10975317B2

Abstract

A process for producing olefin gas from a cracked product effluent, the process comprising the steps of: introducing the cracked product effluent into a fractionator unit, separating the cracked product effluent in the fractionator to produce a cracked light stream and a cracked residuum stream, wherein the cracked light stream comprises olefin gases selected from the group consisting of ethylene, propylene, butylene, and combinations thereof, mixing the cracked residuum stream and a heavy feed in a heavy mixer to produce a combined supercritical process feed, and upgrading the combined supercritical process feed in a supercritical water process to produce Supercritical Water Process (SWP) -treated light products and SWP-treated heavy products, wherein the SWP-treated heavy products comprise a reduced amount of olefins and asphaltenes relative to the cracked residuum stream such that the SWP-treated heavy products exhibit increased stability relative to the cracked residuum stream.

Description

Upgrading of heavy oil for steam cracking process

Technical Field

The invention discloses a method for upgrading petroleum. Specifically, methods and systems for upgrading petroleum using a pretreatment process are disclosed.

Background

Chemical production is a major consumer of crude oil. Traditionally, straight run naphtha, which is a mixture of hydrocarbons boiling below 200 degrees celsius (c), can be used for steam cracking to produce ethylene and propylene because straight run naphtha contains a higher hydrogen content relative to other feedstocks. Further, straight run naphthas typically produce limited amounts of hydrocarbons containing more than 10 carbon atoms, also known as pyrolysis fuel oils, ranging from about 3 weight percent (wt%) to 6 wt% of the total product. Heavier feedstocks such as vacuum gas oils can be processed in a Fluid Catalytic Cracking (FCC) unit to produce propylene and ethylene. Although FCC units can produce high octane gasoline blend stocks, FCC units are limited in the conversion of the feedstock to ethylene and propylene.

Other feedstocks, such as gas oils boiling above 200 ℃, can be used in the steam cracking process, but result in lower yields of ethylene and propylene, and increased coking rates due to heavy molecules in the gas oil fraction. Therefore, the gas oil fraction cannot be used as a suitable feed for a steam cracking process.

The extension of feedstocks for steam cracking processes to include full range crude oil or residual oil fractions is problematic due to the presence of large molecules such as asphaltenes in the feedstock. Heavy molecules, especially polycyclic aromatic compounds, tend to form coke in the pyrolysis tubes and cause fouling in the Transfer Line Exchangers (TLE). The coke layer in the pyrolysis tube inhibits heat transfer and thus may cause physical failure of the pyrolysis tube. Severe coking shortens the run time of the steam cracker, which is one of the most critical parameters controlling the economics of the steam cracker. As a result, the advantages of using cheaper feedstocks, crude oils and heavy residuum streams are offset by the short run length of the steam cracker. It should be noted that the amount of pyrolysis fuel oil may be between 20 and 30 wt.% of the total product stream when starting from a full boiling range crude oil or resid fraction.

The gas oil fraction may be pretreated in one or more pretreatment processes, such as hydrotreating processes, thermal conversion processes, extraction processes, and distillation processes. The thermal conversion process may include a coking process and a visbreaking process. The extraction process may include a solvent deasphalting process. The distillation process may include an atmospheric distillation or a vacuum distillation process. The pretreatment process can reduce heavy residue fractions such as atmospheric residue fractions and vacuum residue fractions. Thus, reducing the heavy residue fraction in the feed to the steam cracking feedstock can increase the efficiency of the steam cracking feedstock.

These pretreatment methods can treat the full range crude oil prior to introducing the pretreatment process into the steam cracking process. The pretreatment process can increase light olefin yields and reduce coking in the steam cracking process. The pretreatment process can increase the hydrogen content of the steam cracking feed, which correlates to the light olefin yield, so that the higher the hydrogen content, the higher the light olefin yield.

Pretreatment methods can reduce the content of heteroatoms such as sulfur and metals. The sulfur compounds may inhibit the formation of carbon monoxide in the steam cracking process by passivating the inner surface of the pyrolysis tube. In one process, 20 ppm by weight of dimethyl sulfide may be added to the sulfur-free feedstock. However, sulfur contents in the feedstock of the steam cracking process of greater than 400 ppm by weight can increase the coking rate in the pyrolysis tube.

While the pretreatment process can improve the efficiency of the steam cracking process, the pretreatment process also has several disadvantages. First, the hydrotreating process may require a large capital investment and may not remove all of the undesirable compounds, such as asphaltenes. Second, the use of pretreatment methods such as coking, extraction, and distillation may result in a reduction in the liquid yield of the feed to the steam cracking process, since a certain amount of the feed will be discarded as a residual oil. Third, the pretreatment process may require extensive maintenance due to catalyst deactivation by coking, asphaltene deposition, catalyst poisoning, fouling, and active material sintering. Finally, many pretreatment processes reject the heaviest fractions of the stream, which reduces the overall yield of light olefins and adversely affects parameters affecting steam cracker economics.

Disclosure of Invention

In a first aspect, a process for producing olefin gas from a cracking product effluent is provided. The method comprises the following steps: introducing the cracked product effluent into a fractionator unit configured to separate the cracked product effluent; separating the cracked product effluent in a fractionator to produce a cracked light stream and a cracked residuum stream, wherein the cracked light stream comprises an olefin gas, wherein the olefin gas is selected from the group consisting of ethylene, propylene, butylene, and combinations thereof; introducing the cracked residuum stream and the heavy feed into a heavy mixer; mixing the cracked residuum stream and the heavy feed in a heavy mixer to produce a combined supercritical process feed; introducing the combined supercritical process feed and water feed to a supercritical water process configured to upgrade the combined supercritical process feed; and in the supercritical water process, upgrading the combined supercritical process feed to produce Supercritical Water Process (SWP) -treated light products and SWP-treated heavy products, wherein the SWP-treated heavy products comprise a reduced amount of olefins and asphaltenes relative to the cracked residuum stream such that the SWP-treated heavy products exhibit increased stability relative to the cracked residuum stream.

In certain aspects, the method further comprises the steps of: introducing the crude oil feed and the hydrogen gas feed into a hydrogen addition process configured to promote hydrogenation of hydrocarbons in the crude oil feed, wherein the hydrogen addition process includes a hydrogenation catalyst, wherein the hydrogenation catalyst is capable of catalyzing a hydrotreating reaction; in a hydrogen addition process, subjecting hydrocarbons in a crude oil feed to a hydrotreating reaction to produce a hydrogenated stream, wherein the hydrogenated stream comprises paraffins, naphthenes, aromatics, light gases, and combinations thereof; introducing the hydrogenated stream into a separator unit configured to separate the hydrogenated stream; separating the hydrogenated stream in a separator unit to produce a light feed and a heavy feed, wherein the light feed comprises hydrocarbons boiling below 650 ° f, wherein the heavy feed comprises hydrocarbons boiling above 650 ° f; introducing a light feed and SWP-treated light products into a light mixer; mixing a light feed with the SWP-treated light product in a light mixer to produce a combined steam cracked feed; introducing the combined steam cracking feed to a steam cracking process configured to thermally crack the combined steam cracking feed in the presence of steam; and in the steam cracking process, causing thermal cracking to occur to produce a cracked product effluent.

In certain aspects, the method further comprises the steps of: introducing the crude oil feed and a hydrogen gas feedstock into a hydrogen addition process configured to promote hydrogenation of hydrocarbons in the crude oil feed, wherein the hydrogen addition process includes a hydrogenation catalyst, wherein the hydrogenation catalyst is capable of catalyzing a hydrotreating reaction; in a hydrogen addition process, subjecting hydrocarbons in a crude oil feed to a hydrotreating reaction to produce a hydrogenated stream, wherein the hydrogenated stream comprises paraffins, naphthenes, aromatics, and light gases; introducing the hydrogenated stream and the SWP-treated light product into a feed mixer; mixing the light feed with the SWP-treated light product in a feed mixer to produce a combined separator feed; introducing the combined separator feed into a separator unit configured to separate the combined separator feed; separating the combined separator feed in a separator unit to produce a light feed and a heavy feed, wherein the light feed comprises hydrocarbons boiling less than 650 ° f, wherein the heavy feed comprises hydrocarbons boiling greater than 650 ° f; introducing the light feed to a steam cracking process configured to thermally crack the light feed in the presence of steam; and in the steam cracking process, causing thermal cracking to occur to produce a cracked product effluent.

In certain aspects, the method further comprises the steps of: separating light gases from the cracked product effluent in a fractionator unit to produce a recovered hydrogen stream, wherein the recovered hydrogen stream comprises hydrogen; and introducing the recovered hydrogen stream into a heavy mixer such that the combined supercritical water feed comprises hydrogen.

In certain aspects, the crude oil feed has an API gravity between 15 and 50, wherein the atmospheric fraction of the crude oil feed is between 10% and 60% by volume, wherein the vacuum fraction is between 1% and 35% by volume, wherein the asphaltene fraction is between 0.1% and 15% by weight, and wherein the total sulfur content is between 2.5% and 26% by volume. In certain aspects, the hydrogenation catalyst comprises a transition metal sulfide supported on an oxide support, wherein the transition metal sulfide is selected from the group consisting of cobalt molybdenum sulfide (CoMoS), nickel molybdenum sulfide (NiMoS), nickel tungsten sulfide (NiWS), and combinations thereof. In certain aspects, the hydrotreating reaction is selected from the group consisting of a hydrogenation reaction, a hydrodedissociation reaction, a hydrocracking reaction, an isomerization reaction, an alkylation reaction, an upgrading reaction, and combinations thereof. In certain aspects, the cracked resid stream comprises hydrocarbons boiling above 200 ℃.

In a second aspect, there is provided a process for producing olefin gas from a cracking product effluent, the process comprising the steps of: introducing the cracked product effluent into a fractionator unit configured to separate the cracked product effluent; separating the cracked product effluent in a fractionator to produce a cracked light stream and a cracked residuum stream, wherein the cracked light stream comprises an olefin gas, wherein the olefin gas is selected from the group consisting of ethylene, propylene, butylene, and combinations thereof; introducing the cracked residue stream and the distillate residue stream into a heavy mixer; mixing the cracked residue stream and the distillate residue stream in a heavy mixer to produce a combined residue stream; introducing the combined resid stream and a water feed to a supercritical water process configured to upgrade the combined resid stream; and upgrading the combined resid stream in a supercritical water process to produce SWP-treated light products and SWP-treated heavy products, wherein the SWP-treated heavy products comprise a reduced amount of olefinic asphaltenes relative to the cracked resid stream, such that the SWP-treated heavy products exhibit increased stability relative to the cracked resid stream.

In certain aspects, the method further comprises the steps of: introducing a crude oil feed to a distillation unit configured to separate the crude oil feed; separating the crude oil feed in a distillation unit to produce a distillate oil stream and a distillate residuum stream, wherein the distillate oil stream comprises hydrocarbons boiling at less than 650 ° f; introducing the distillate oil stream to a hydro-addition process configured to promote hydrogenation of hydrocarbons in the distillate oil stream, wherein the hydro-addition process includes a hydrogenation catalyst, wherein the hydrogenation catalyst is capable of catalyzing a hydrotreating reaction; in a hydro-addition process, subjecting hydrocarbons in a distillate oil stream to a hydrotreating reaction to produce a hydrogenated stream, wherein the hydrogenated stream comprises paraffins, naphthenes, aromatics, light gases, and combinations thereof; introducing the hydrogenated stream and the SWP-treated light product into a feed mixer; mixing the hydrogenated stream and the SWP-treated light products in a feed mixer to produce a combined separator feed; introducing the combined separator feed to a steam cracking process configured to thermally crack the combined separator feed in the presence of steam; and in the steam cracking process, causing thermal cracking to occur to produce a cracked product effluent.

In certain aspects, the method further comprises: introducing a crude oil feed to a distillation unit configured to separate the crude oil feed; separating the crude oil feed in a distillation unit to produce a distillate oil stream and a distillate residuum stream, wherein the distillate oil stream comprises hydrocarbons boiling at less than 650 ° f; introducing a distillate oil stream and the SWP-treated light products into a distillate mixer; mixing the distillate oil stream and the SWP treated light products in a distillate mixer to produce a combined distillate oil stream; introducing the combined distillate oil stream to a hydro-addition process configured to promote hydrogenation of hydrocarbons in the combined distillate oil stream, wherein the hydro-addition process comprises a hydrogenation catalyst, wherein the hydrogenation catalyst is capable of catalyzing a hydrotreating reaction; subjecting hydrocarbons in the combined distillate oil stream to a hydrotreating reaction in a hydrogen addition process to produce a hydrogenated stream, wherein the hydrogenated stream comprises paraffins, naphthenes, aromatics, light gases, and combinations thereof; introducing the hydrogenated stream into a steam cracking process configured to thermally crack the hydrogenated stream in the presence of steam; and in the steam cracking process, causing thermal cracking to occur to produce a cracked product effluent.

In a third aspect, a process for producing olefin gas from a cracking product effluent is provided. The method comprises the following steps: introducing the cracked product effluent into a fractionator unit configured to separate the cracked product effluent; separating the cracked product effluent in a fractionator to produce a cracked light stream and a cracked residuum stream, wherein the cracked light stream comprises an olefin gas, wherein the olefin gas is selected from the group consisting of ethylene, propylene, butylene, and combinations thereof; introducing the cracked residuum stream and the hydrogenation stream into a heavy mixer; mixing the cracked residue stream and the hydrogenated stream in a heavy mixer to produce a mixed stream; introducing the mixed stream and a water feed into a supercritical water process configured to upgrade the mixed stream; and in the supercritical water process, upgrading the mixed stream to produce Supercritical Water Process (SWP) -treated light products and SWP-treated heavy products, wherein the SWP-treated heavy products comprise a reduced amount of olefins and asphaltenes relative to the cracked residuum stream such that the SWP-treated heavy products exhibit increased stability relative to the cracked residuum stream.

In certain aspects, the method further comprises the steps of: introducing a crude oil feed to a distillation unit configured to separate the crude oil feed; separating the crude oil feed in a distillation unit to produce a distillate oil stream and a distillate residuum stream, wherein the distillate oil stream comprises hydrocarbons boiling at less than 650 ° f; introducing a distillate oil stream and the SWP-treated light products into a distillate mixer; mixing the distillate oil stream and the SWP treated light products in a distillate mixer to produce a combined distillate oil stream; introducing the combined distillate oil stream into a steam cracking process configured to thermally crack the combined distillate oil stream in the presence of steam; in a steam cracking process, causing thermal cracking to occur to produce a cracked product effluent; introducing the distillate residue stream to a hydro-addition process configured to promote hydrogenation of hydrocarbons in the distillate residue stream, wherein the hydro-addition process comprises a hydrogenation catalyst, wherein the hydrogenation catalyst is capable of catalyzing a hydrotreating reaction; and subjecting the hydrocarbons in the distillate residuum stream to a hydrotreating reaction in a hydrogen addition process to produce a hydrogenated stream, wherein the hydrogenated stream comprises paraffins, naphthenes, aromatics, light gases, and combinations thereof.

Drawings

These and other features, aspects, and advantages that are within the scope of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings. It is to be noted, however, that the appended drawings illustrate only a few embodiments and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

Figure 1 provides a flow diagram of an embodiment of an upgrading process.

Figure 2 provides a flow diagram of an embodiment of an upgrading process.

Figure 3 provides a flow diagram of an embodiment of an upgrading process.

Figure 4 provides a flow diagram of an embodiment of an upgrading process.

FIG. 5 provides a flow diagram of an embodiment of an upgrading process.

Figure 6 provides a flow diagram of an embodiment of an upgrading process.

Figure 7 provides a flow diagram of an embodiment of an upgrading process.

FIG. 8 provides a flow diagram of an embodiment of an upgrading process.

Figure 9 provides a flow diagram of a comparative system without a supercritical water process.

In the drawings, like components or features, or both, may have like reference numerals.

Detailed Description

Although the scope of the apparatus and method has been described with several embodiments, it is understood that one of ordinary skill in the relevant art will recognize that many examples, variations, and modifications of the apparatus and method described herein are within the scope and spirit of the embodiments.

Thus, the described embodiments are set forth without any loss of generality to, and without imposing limitations upon, the embodiments. It will be appreciated by a person skilled in the art that the scope of the present invention includes all possible combinations and uses of the specific features described in the specification.

The described processes and systems relate to upgrading a crude oil feedstock. The process provides a method and apparatus for upgrading heavy fractions from a steam cracking process. The process provides a process and apparatus for producing light olefins. Advantageously, the upgrading process described herein can increase the overall efficiency of the steam cracking process by cracking heavy fractions, such as asphaltenes, prior to introducing such heavy fractions into the steam cracking process, where such heavy fractions are not suitable for the steam cracking process. Advantageously, the upgrading process increases the overall efficiency of light olefins production from full range crude oil. Advantageously, the upgrading process described herein increases the overall efficiency of the steam cracking process by upgrading the heavy fraction from the steam cracking process. The introduction of the supercritical water process can upgrade the heavy fraction from the steam cracking process, thereby enabling the supercritical treated stream to be reintroduced into the steam cracker. Advantageously, the introduction of the supercritical water process can increase liquid yield compared to conventional thermal processes because the supercritical water process suppresses solid coke formation and gas formation. Advantageously, the introduction of a supercritical water process can crack and depolymerize asphaltenes and reduce stress on the hydroprocessing unit to prevent severe deactivation in the hydroprocessing unit, which can extend the life cycle of the catalyst and reduce catalyst maintenance.

As used throughout, "external supply of hydrogen" means that hydrogen is added to the feed to the reactor or to the reactor itself. For example, a reactor without external supply of hydrogen means that the feed to the reactor and the reactor are not fed with gaseous hydrogen (H)₂) Or liquid hydrogen, so that there is no hydrogen (as H)₂In the form of) is the feed or a portion of the feed to the reactor.

As used throughout, "external supply of catalyst" refers to the addition of catalyst to the feed to the reactor or the presence of catalyst in the reactor, such as a fixed bed catalyst in the reactor. For example, an externally supplied reactor without catalyst means that no catalyst is added to the feed to the reactor and the reactor does not include a catalyst bed in the reactor.

As used throughout, "atmospheric fraction" or "atmospheric residuum fraction" refers to a fraction of an oil-containing stream having a T10% of 650 ° f such that 90% by volume of the hydrocarbons boil above 650 ° f and include vacuum residuum fractions. The atmospheric fraction may comprise distillate oil from atmospheric distillation.

As used throughout, "vacuum fraction" or "vacuum residue fraction" refers to a fraction of an oil-containing stream having a T10% of 1050 ° f.

As used throughout, "asphaltenes" refer to fractions of an oil-containing stream that are insoluble in n-alkanes, particularly n-heptane.

As used throughout, "light hydrocarbons" refers to hydrocarbons having less than 9 carbon atoms (C)_9-Hydrocarbons).

As used throughout, "heavy hydrocarbon" refers to hydrocarbons having 9 or more carbon atoms (C)₉₊)。

As used throughout, "hydrogenation" refers to the addition of hydrogen to a hydrocarbon compound.

As used throughout, "coke" refers to toluene-insoluble material present in petroleum.

As used throughout, "cracking" refers to the breaking of hydrocarbons into smaller hydrocarbons containing few carbon atoms due to the breaking of carbon-carbon bonds.

As used throughout, "heteroatom" refers to sulfur, nitrogen, oxygen, and metals, either alone or as heteroatom-hydrocarbon compounds.

As used throughout, "upgrading" refers to one or both of the following: increasing the API gravity, decreasing the amount of heteroatoms, decreasing the amount of asphaltenes, decreasing the amount of atmospheric fractions, increasing the amount of light fractions, decreasing the viscosity, and combinations thereof, in the process outlet stream relative to the process feed stream. One skilled in the art will appreciate that upgrading may be of relative significance such that a stream may be upgraded compared to another stream, but may still contain undesirable components, such as heteroatoms.

As used throughout, "conversion reactions" refer to reactions that can upgrade a hydrocarbon stream, including cracking, isomerization, alkylation, dimerization, aromatization, cyclization, desulfurization, denitrification, deasphalting, and demetallization.

As used throughout, "stable" or "stability" refers to the quality of the hydrocarbon and the ability of the hydrocarbon to resist degradation, oxidation, and contamination. The stability of a hydrocarbon is related to the amount of asphaltenes and olefins (particularly diolefins) present in the hydrocarbon. Increased amounts of asphaltenes and olefins can lead to reduced stability of the oil, as asphaltenes and olefins are more prone to degradation, oxidation and fouling. Stability is typically determined by ASTM7060 for fuel oils and ASTM D381 for gasoline (gum formation). Stability includes storage stability.

As used throughout, "distillate" refers to hydrocarbons boiling below 650F. Distillate oils may include distillable materials from atmospheric distillation processes. Examples of hydrocarbons in the distillate may include naphtha, gasoline, kerosene, diesel, and combinations thereof.

The following embodiments, provided with reference to the figures, describe the upgrading process.

Referring to fig. 1, a process flow diagram of an upgrading process is provided. Crude oil feed 5 is introduced into separator unit 100. Crude feed 5 may be any full range crude containing hydrocarbons, crude feed 5 having an API gravity between about 15 and about 50, an atmospheric fraction between about 10 volume percent (vol%) and about 60 vol%, a vacuum fraction between about 1 vol% and about 35 vol%, an asphaltene fraction between about 0.1 weight percent (wt%) and about 15 wt%, and a total sulfur content between about 0.02 wt% and about 4 wt%. In at least one embodiment, the crude oil feed 5 may have an API gravity between about 24 and about 49, an atmospheric fraction between about 20 and about 57 vol%, a vacuum fraction between about 2.5 and about 26 vol%, an asphaltene fraction between about 0.2 and about 11 wt%, and a total sulfur content between about 0.05 and about 3.6 wt%. In at least one embodiment, crude feed 5 has an API gravity between 23 and 27, an atmospheric fraction of less than about 24% by volume, and a total sulfur content of about 2.8% by weight.

The separator unit 100 can be any type of unit capable of fractionating these streams into two or more streams based on the boiling point or boiling point range of the full boiling range crude oil. Examples of separator unit 100 may include a distillation unit, a flash column, and combinations thereof. The operating conditions of the separator unit 100 may be selected based on the desired number and composition of the separated streams. The desired composition of the separated stream may depend on the unit of operation downstream of the separator unit 100. The separator unit 100 can separate the crude oil feed 5 to produce a light feed 10 and a heavy feed 15.

The light feed 10 may comprise hydrocarbons boiling less than 650 ° f. In at least one embodiment, the light feed 10 is free of asphaltenes. The operating conditions of the separator unit 100 may produce a light feed 10 having an increased amount of paraffins compared to the crude oil feed 5, making the light feed 10 suitable as a direct feed to a steam cracking process. The increased paraffins increase the olefins produced in the steam cracking process. Advantageously, the reduced boiling point of the light feed 10 reduces the tendency for coke formation in the steam cracking process as compared to fluids having higher boiling points.

Heavy feed 15 may comprise hydrocarbons boiling above 650 ° f.

The light feed 10 may be introduced into a light mixer 110. Light mixer 110 may be any type of mixing device capable of mixing two or more hydrocarbon streams. The light weight mixer 110 may include an inline mixer, a static mixer, a mixing valve, and a stirred tank mixer. Light feedstock 10 can be mixed with Supercritical Water Process (SWP) treated light products 50 in a light mixer 110 to produce a combined steam cracked feedstock 20.

The combined steam cracking feed 20 may be introduced to the steam cracking process 200. The steam cracking process 200 may be any process capable of thermally cracking a hydrocarbon stream in the presence of steam. Steam may be used to dilute the hydrocarbons to increase olefin formation and reduce coke formation. The steam cracking process 200 may include a cracking furnace, cracking tubes, heat exchangers, compressors, refrigeration systems, gas separation units, and other steam cracking units. The steam cracking process 200 may include free radical reactions, which may be characterized by a number of chain reactions.

The steam cracking process 200 can produce a cracked product effluent 25. The cracked product effluent 25 can be introduced into the fractionator unit 300.

The fractionator unit 300 may be any type of unit capable of fractionating the cracked product effluent 25 into two or more streams. Examples of fractionator unit 300 may include distillation units, flash columns, quench units, dehydration units, acid gas processing, refrigeration units, and combinations thereof. The operating conditions of the fractionator unit 300 may be selected based on the desired number and composition of the separated streams. In at least one embodiment, the fractionator unit 300 may include a quench unit, a dehydration unit, and acid gas treatment to remove hydrogen sulfide and carbon dioxide, followed by a chiller unit, wherein the gas stream may be cooled by a refrigeration unit to about-140 ℃ and-160 ℃ to condense olefin gases, which separate the olefin gases from the light gases. Fractionator unit 300 may separate cracked product effluent 25 to produce cracked lights stream 30 and cracked resid stream 35.

Cracked light stream 30 may comprise light gases, olefin gases, light hydrocarbons, and combinations thereof. The light gas may include hydrogen, carbon monoxide, oxygen, and combinations thereof. The light gas may be comprised between 80 mole percent (mol%) and 95 mol%. The olefin gas may include ethylene, propylene, butylene, and combinations thereof. The composition of cracked lights stream 30 may depend on the composition of crude oil feed 5, the units included in the upgrading process, and the reactions occurring in the units of the upgrading process. The hydrogen content in crude oil feed 5 may be between 0.1 wt% and 1 wt%. The carbon monoxide content in the cracked product effluent 25 can be between 100 parts per million by weight (wt ppm) and 1,000 wt ppm.

Cracked lights stream 30 may be used as a product stream, sent to storage, further processed, or blended in downstream processes. Further processing may include separating the cracked light stream 30 to produce a purified ethylene stream, a purified propylene stream, a purified mixed ethylene and propylene stream, a mixed butane, and combinations thereof.

The cracked raffinate stream 35 may include hydrocarbons having boiling points greater than 200 ℃. In at least one embodiment, the cracked resid stream 35 comprises olefins, aromatics, asphaltenes, heteroatoms, and combinations thereof. Heteroatoms can include nitrogen compounds, vanadium, iron, chloride, oxygen-containing compounds, non-hydrocarbon particulates, and combinations thereof. In at least one embodiment, the cracked resid stream 35 can comprise hydrocarbons containing ten or more carbons (C10+ hydrocarbons). In at least one embodiment, the cracked resid stream 35 comprises pyrolysis fuel oil. The cracked residuum stream 35 may be introduced into the heavy mixer 120.

Heavy mixer 120 may be any type of mixing unit capable of mixing two or more hydrocarbon streams. Examples of the heavy mixer 120 may include an inline geometric mixer (inline geometric mixer), a static mixer, a mixing valve, and a stirred tank mixer. The cracked residuum stream 35 may be mixed with the heavy feed 15 to produce a combined supercritical process feed 40.

The combined supercritical process feed 40 can be introduced to the supercritical water process 400 along with the water feed 45. The water feed 45 may be demineralized water having a conductivity of less than 1.0 microsiemens per centimeter (μ S/cm), alternatively less than 0.5 μ S/cm, alternatively less than 0.1 μ S/cm. In at least one embodiment, the water feed 45 is demineralized water having an electrical conductivity of less than 0.1 μ S/cm. The sodium content of the water feed 45 may be less than 5 micrograms/liter (μ g/L), or less than 1 μ g/L. The chloride content of the water feed 45 may be less than 5 μ g/L, or less than 1 μ g/L. The silicon content of the water feed 45 may be less than 3 μ g/L.

The cracked residue stream 35 may be unstable due to the presence of olefins and asphaltenes, making the cracked residue stream 35 unsuitable for use as a fuel oil stream without removal of olefins, including diolefins. The supercritical water process 400 can convert olefins and diolefins in the combined supercritical water process feed 40 to aromatics and can remove asphaltenes. Advantageously, treating the cracked residuum stream 35 in the supercritical water process 400 increases the yield of the crude oil feed 5. Treating the cracked residuum stream 35 in the supercritical water process 400 improves the stability of the hydrocarbons in the SWP-treated heavy products 55 as compared to cracking the hydrocarbons in the residuum stream 35. Advantageously, treating the cracked residuum stream 35 converts low value hydrocarbons to higher value hydrocarbons, thereby increasing the overall value of the crude oil feed.

Supercritical water process 400 can be any type of hydrocarbon upgrading unit that facilitates the reaction of hydrocarbons in the presence of supercritical water. Supercritical water processes may include reactors, heat exchangers, pumps, separators, pressure control systems, and other devices. Supercritical water process 400 may include one or more reactors, where the reactors operate at the following conditions: the temperature is between 380 ℃ and 450 ℃, the pressure is between 22MPa and 30MPa, the residence time is between 1 minute and 60 minutes, and the water-to-oil ratio at standard ambient temperature and pressure is between 1:10 v/v and 1:0.1 v/v. In at least one embodiment, the supercritical water process 400 may be absent an external supply of hydrogen. The supercritical water process 400 may be absent an external supply of catalyst.

It is known in the art that hydrocarbon reactions in supercritical water upgrade heavy oils and crude oils containing sulfur compounds, producing products with lighter fractions. Supercritical water has unique properties that make it suitable for use as a petroleum reaction medium where reaction objectives may include conversion reactions, desulfurization reactions, denitrification reactions, and demetallization reactions. Supercritical water is water having a temperature equal to or greater than the critical temperature of water and a pressure equal to or greater than the critical pressure of water. The critical temperature of water is 373.946 ℃. The critical pressure of water is 22.06 megapascals (MPa). Advantageously, under supercritical conditions, water acts as both a source of hydrogen and a solvent (diluent) in the conversion, desulfurization and demetallization reactions, and no catalyst is required. Hydrogen from water molecules is transferred to the hydrocarbons by direct transfer or by indirect transfer (such as the water gas shift reaction). In the water gas shift reaction, carbon monoxide and water react to produce carbon dioxide and hydrogen. Hydrogen may be transferred to hydrocarbons in desulfurization reactions, demetallization reactions, denitrification reactions, and combinations thereof. Hydrogen can also reduce the olefin content. The internal supply of hydrogen generation can reduce coke formation.

Without being bound by a particular theory, it is understood that the basic reaction mechanism of supercritical water mediated petroleum processes is the same as the radical reaction mechanism. The free radical reaction includes initiation, propagation, and termination steps. For hydrocarbons, such as C in particular₁₀₊Such as heavy molecules, initiation is the most difficult step and conversion in supercritical water may be limited due to the high activation energy required for initiation. Initiating the cleavage of the desired chemical bond. The bond energy of the carbon-carbon bond is about 350kJ/mol, and the bond energy of the carbon-hydrogen bond is about 420 kJ/mol. Due to chemical bond energy, carbon-carbon bonds and carbon-hydrogen bonds are not easily broken at supercritical water process temperatures of 380 ℃ to 450 ℃ without catalysts or free radical initiators. In contrast, the bond energy of the aliphatic carbon-sulfur bond is about 250 kJ/mol. Aliphatic carbon-to-sulfur bonds (e.g. thiols, sulphurisation)Object and disulfide) than aromatic carbon-sulfur bonds.

Thermal energy generates free radicals through chemical bond cleavage. Supercritical water produces a "cage effect" by surrounding free radicals. The radicals surrounded by water molecules cannot easily react with each other, and thus the intermolecular reaction contributing to the formation of coke is suppressed. The cage effect inhibits coke formation by limiting the reactions between free radicals. Supercritical water having a low dielectric constant dissolves hydrocarbons and surrounds radicals to prevent a reaction between the radicals, which is a termination reaction causing condensation (dimerization or polymerization). Because the supercritical water cage provides a barrier, hydrocarbon radical transfer in supercritical water is more difficult than in conventional thermal cracking processes such as delayed coking where radicals move freely without such a barrier.

The sulfur compounds liberated from the sulfur-containing molecule can be converted to H₂S, mercaptans and elemental sulphur. Without being bound by a particular theory, it is believed that hydrogen sulfide is similar to water (H) due to its small size and similarity to water₂O) without being "impeded" by supercritical water cages. Hydrogen sulfide can freely pass through the supercritical water cage to grow radicals and distribute hydrogen. Hydrogen sulfide may lose its hydrogen due to its hydrogen abstraction reaction with hydrocarbon radicals. The resulting Hydrogen Sulfur (HS) radicals are able to abstract hydrogen from the hydrocarbon, which will allow more radicals to be formed. Thus, H in radical reactions₂S acts as a transfer agent to transfer radicals and abstract/donate hydrogen.

Supercritical water process 400 can upgrade combined supercritical process feed 40 to produce SWP-treated light products 50 and SWP-treated heavy products 55. The amount of waste feedstock is one of the economic parameters of a steam cracker.

The SWP-treated light products 50 may include hydrocarbons boiling below 650 ° f. Advantageously, the SWP treated light product 50 is suitable for processing in the steam cracking process 200. The SWP-treated light product 50 may be introduced into a light mixer 110.

SWP treated heavy product 55 may comprise hydrocarbons boiling above 650 ° f. The amount and composition of SWP treated heavy product 55 depends on the feedstock and operating conditions. SWP treated heavies 55 may exhibit increased stability as compared to cracked resid stream 35 due to reduced amounts of olefins (including diolefins) and asphaltenes. The cracked resid stream 35 can contain a reduced amount of sulfur and a reduced amount of polynuclear aromatics content as compared to SWP-treated heavies 55. SWP treated heavy product 55 may be introduced into a fuel tank or may be further processed. In at least one embodiment, SWP treated heavy product 55 is further processed in a delayed coker.

Referring to fig. 2, an embodiment of an upgrading process is described with reference to fig. 1. Crude oil feed 5 is introduced into the hydrogen addition process 500 along with hydrogen feed 65. The hydrogen feed 65 can be any external supply of hydrogen that can be introduced into the hydrogen addition process 500. The hydrogen feed 65 may originate from a naphtha reforming unit, a methane reforming unit, a recycle hydrogen stream from the hydrogen addition process 500, a recycle hydrogen stream from another refinery unit such as a hydrocracker, or any other source. The purity of the hydrogen feed 65 may depend on the composition of the crude oil feed 5 and the catalyst in the hydrogen addition process 500.

The hydrogen addition process 500 can be any type of processing unit capable of facilitating the hydrogenation of crude oil in the presence of hydrogen. In at least one embodiment, the hydrogen addition process 500 is a hydrotreating process. The hydrogen addition process 500 may include pumps, heaters, reactors, heat exchangers, hydrogen feed systems, product gas desulfurization units, and other unit units included in the hydroprocessing process. The hydrogen addition process 500 can include a hydrogenation catalyst. The hydrogenation catalyst may be designed to catalyze a hydrotreating reaction. The hydrotreating reaction may include hydrogenation reactions, hydro-dissociation reactions, hydrocracking reactions, isomerization reactions, alkylation reactions, upgrading reactions, and combinations thereof. The hydro-dissociation reaction can remove heteroatoms. The hydrogenation reaction can produce saturated hydrocarbons from aromatic hydrocarbons and olefinic compounds. Upgrading reactions may include hydrodesulfurization reactions, hydrodemetallation reactions, hydrodenitrogenation reactions, hydrocracking reactions, hydroisomerization reactions, and combinations thereof. In at least one embodiment, the hydrotreating catalyst may be designed to catalyze a combination of a hydrogenation reaction and an upgrading reaction.

The catalyst may comprise a transition metal sulphide supported on an oxide support. The transition metal sulfide may comprise cobalt, molybdenum, nickel, tungsten, and combinations thereof. Transition metal sulfides may include cobalt molybdenum sulfide (CoMoS), nickel molybdenum sulfide (NiMoS), nickel tungsten sulfide (NiWS), and combinations thereof. The oxide support material may include alumina, silica, zeolites, and combinations thereof. The oxide support materials may include gamma-alumina, amorphous silica-alumina, and alumina-zeolites. The oxide support material may include dopants such as boron and phosphorus. The oxide support material may be selected based on textural properties (such as surface area and pore size distribution, surface properties such as acidity, and combinations thereof). When used to treat heavy crude oil, the pore size may be large, in the range of 10nm to 100nm, to reduce or prevent pore plugging due to heavy molecules. The oxide support material may be porous to increase surface area. The surface area of the oxide support material may be in the range of 100m²G and 1000m²In the range of/g, or in the range of 150m²G and 400m²In the range of/g. The acidity of the catalyst can be controlled to prevent over-cracking of hydrocarbons and reduce coking on the catalyst while maintaining catalyst activity.

The hydrogen addition process 500 can include one or more reactors. The reactors may be arranged in series or in parallel. In at least one embodiment, the hydrogen addition process 500 includes more than one reactor, where the reactors are arranged in series, and the hydrogenation and upgrading reactions are arranged in different reactors to maximize the life of the catalyst in each reactor.

The arrangement of equipment and operating conditions in the hydrogen addition process 500 can be selected to maximize the yield of liquid product. In at least one embodiment, the hydrogen addition process 500 can be arranged and operated to maximize the liquid yield in the hydrogenated stream 60. The hydrogen content and hydrogen to carbon ratio of hydrogenated stream 60 may be greater than the hydrogen content and hydrogen to carbon ratio of crude oil feed 5. In at least one embodiment, the hydrogen addition process 500 can be configured and operated to reduce the amount of heteroatoms relative to the crude oil feed 5 and increase the amount of distillate. The hydrogenated stream 60 can be introduced to a separator unit 100. The hydrogenated stream 60 may comprise paraffins, naphthenes, aromatics, light gases, and combinations thereof. The light gas may include light hydrocarbons, hydrogen sulfide, and combinations thereof. In at least one embodiment, the hydrogenated stream 60 may comprise olefins present in an amount less than 1 wt.%.

As depicted in fig. 1, the hydrogenated stream 60 may be separated in a separator unit 100 to produce a light feed 10 and a heavy feed 15.

The hydro-addition process 500 can reduce heavy fractions in the hydrogenated stream 60 relative to the crude oil feed 5, but atmospheric fractions can remain in the hydrogenated stream 60, including asphaltenes. Combining the hydrogen addition process 500 with the separator unit 100 can remove atmospheric fractions from the hydrogenated stream 60 to produce a light feed 10 that can be introduced to the steam cracking process 200. Advantageously, introducing heavy feed 15 into supercritical water process 400 may reduce the amount of atmospheric fractions in heavy feed 15. Advantageously, SWP-treated light products 50 may be absent atmospheric fractions, which enables SWP-treated light products 50 to be recycled to steam cracking process 200, which increases the overall yield from steam cracking process 200 compared to a process without upgrading heavy fractions by hydrogen addition process 500. Advantageously, the supercritical water process 400 can reduce the amount of asphaltenes in the heavy feed 15.

Referring to fig. 3, an alternative embodiment of the upgrading process is described with reference to fig. 2. The hydrogenated stream 60 is introduced into a feed mixer 130. The feed mixer 130 may be any type of mixing unit capable of mixing two or more hydrocarbon streams. Examples of the feed mixer 130 may include inline mixers, static mixers, mixing valves, and stirred tank mixers. In the feed mixer 130, the hydrogenated stream 60 is mixed with the SWP treated light product 50 to produce a combined separator feed 70. The combined separator feed 70 is introduced into a separator unit 100. Advantageously, routing of SWP-treated light products 50 may allow for the design of such separators in supercritical water process 400: loss of valuable light ends is minimized by using the wide boiling point range of SWP-treated light products 50.

Referring to fig. 4, an alternative embodiment of the upgrading process is described with reference to fig. 3. The fractionator unit 300 can separate light gases from the cracked product effluent 25 to produce a recovered hydrogen stream 75 in addition to the cracked light stream 30 and the cracked bottoms stream 35. The recovered hydrogen stream 75 may be introduced to a supercritical water process 400. In at least one embodiment, the recovered hydrogen stream 75 may be introduced to the heavy mixer 40. Introducing recycled hydrogen into the supercritical water process 400 may improve the reaction conditions in the supercritical water process 400 by increasing the saturated hydrocarbon radical reaction, inducing cracking of macromolecules, inhibiting the dehydrogenation reaction from producing hydrogen, and increasing the asphaltene conversion reaction, the desulfurization reaction, and the denitrification reaction. Although described with reference to the embodiment shown in fig. 4, one skilled in the art will appreciate that in the various embodiments described herein and obtained with reference to the figures, the recovered hydrogen stream 75 may be produced by the fractionator unit 300.

Referring to fig. 5, an alternative embodiment of the upgrading process is described with reference to fig. 2 and 3. Crude oil feed 5 may be introduced into distillation unit 600. Distillation unit 600 may be any type of distillation column capable of separating a hydrocarbon stream into one or more streams based on the boiling of a desired product stream. The distillation unit 600 may separate the crude oil feed 5 into a distillate oil stream 80 and a distillate residue oil stream 85. The distilled residuum stream 85 may contain hydrocarbons boiling above 650 ° f in the crude oil feed 5. The distillate oil stream 80 can include hydrocarbons boiling below 650 ° f in the crude oil feed 5. The distillate oil stream 80 can be introduced to the hydro-addition process 500. The hydro-addition process 500 can add hydrogen to the hydrocarbons in the distillate oil stream 80 to produce the hydrogenated stream 60. The hydrogen content and hydrogen to carbon ratio of the hydrogenated stream 60 may be greater than the hydrogen content and hydrogen to carbon ratio of the distillate stream 80. Advantageously, separating the distillate residuum stream 85 and treating the distillate residuum stream 85 in the supercritical water process 400 may remove high boiling point compounds by treatment in the hydrogen addition process 500, which may reduce the amount of hydrogen used in the hydrogen addition process 500 and may extend the life of the catalyst in the same process. In summary, the channeling of high boilers by the hydrogen addition process 500 improves process economics, reduces equipment footprint, and extends catalyst life due to reduced hydrogen consumption. The hydrogenated stream 60 can be introduced to a feed mixer 130.

The combined separator feed 70 can be introduced to the steam cracking process 200. The distillate residue oil stream 85 can be mixed with the cracked residue stream 35 in a heavy mixer 120 to produce a combined residue stream 90. The combined residuum stream 90 may be introduced to the supercritical water process 400.

Referring to fig. 6, an alternative embodiment of the upgrading process is described with reference to fig. 1, 2 and 5. In the distillate mixer 140, the distillate oil stream 80 is mixed with the SWP-treated light products 50 to produce a combined distillate oil stream 95. The distillate mixer 140 can be any type of mixing unit capable of mixing two or more hydrocarbon streams. Examples of the distillate mixer 140 may include inline mixers, static mixers, mixing valves, and stirred tank mixers. The SWP-treated light product 50 may contain a quantity of olefins that may be saturated into paraffins by treatment in the hydrogen addition process 500. The combined distillate oil stream 95 can be introduced to a hydrogen addition process 500. Advantageously, the treatment of the distillate residuum stream 85 in the supercritical water process may reduce the amount of asphaltenes, metals, and micro-carbon in the SWP treated light products 50 as compared to the amount in the distillate residuum stream 85, thereby enabling a longer run period in the hydrogen addition process 500 at a sustained performance level. Advantageously, introducing SWP-treated light product 50 to the hydro-addition process 500 can increase the olefin content of the cracked product effluent 25, as the increased amount of paraffins in the hydrogenated stream 60 increases the olefin content of the cracked product effluent 25. Hydrogenation is more favored with smaller molecules, so a greater amount of hydrogen can be added to the heavier fraction after treatment with supercritical water than in the embodiment of fig. 5.

Referring to fig. 7, an embodiment of an upgrading process is provided with reference to fig. 1, 2, 5, and 6. The distillate residuum stream 85 is introduced into the hydrogen addition process 500 along with the hydrogen feed 65. The hydrogen addition process 500 can produce a hydrogenated stream 60. The hydrogenation stream 60 is described with reference to fig. 2. Advantageously, treating hydrogenated stream 60 in supercritical water process 400 may produce a greater amount of saturated hydrocarbons in SWP treated light product 50 than well SWP treated heavy product 55 due to the presence of hydrogen in hydrogenated stream 60. As previously described, the presence of hydrogen in the supercritical water process 400 may increase the number of saturated hydrocarbon radical reactions, induce cracking of macromolecules, and increase asphaltene conversion reactions, desulfurization reactions, and denitrification reactions. Hydrogenated stream 60 can be mixed with cracked resid stream 35 in heavy mixer 120 to produce mixed stream 92. Mixed heavy stream 92 may be introduced to supercritical water process 400. The distillate oil stream 80 can be introduced to the steam cracking process 200 as part of the combined distillate oil stream 95 without further treatment.

Referring to fig. 8, an embodiment of the upgrading process is described with reference to fig. 1, 2, 5, 6, and 7. The hydrogen addition process 500 can include a means for separating the hydrogenated stream to produce a hydrogenated heavy product 62 and a hydrogenated light product 64. The hydrogenated light products 64 can be mixed with the distillate oil stream 80 and SWP-treated light products 50 in a distillate mixer 140 such that the hydrogenated light products are sent to the steam cracking process 200 as part of the combined distillate oil stream 95.

In heavy mixer 120, hydrogenated heavy product 62 is mixed with cracked resid stream 35 to produce mixed heavy stream 94.

Advantageously, the embodiments described herein accommodate the use of a wider range of feedstocks as crude feed 5 than steam cracking processes alone. In processes where the steam cracker is followed by a supercritical water process, the supercritical water process can treat the steam cracker effluent to remove sulfur, remove metals, reduce asphaltenes, and reduce viscosity. However, high viscosity oils cannot be processed directly in a steam cracker. Furthermore, unless the feedstock has a high content of olefins, the liquid yield of the feedstock directly introduced into the steam cracking process may be reduced. In the upgrading process of the embodiments described herein, the heavy fraction is first separated and treated in a supercritical water process, which can upgrade the heavy fraction to remove sulfur, remove metals, reduce asphaltenes, reduce viscosity, and increase the amount of light olefins as compared to the heavy fraction. Thus, the upgrading process described herein can treat high viscosity oils and can increase the fraction of light olefins in the feed to the steam cracker.

Additional devices such as storage tanks may be used to contain the feed to each unit. Instruments may be included on the production line to measure various parameters, including temperature, pressure, and water concentration.

Examples

Example is a comparative example comparing the comparative process implemented in figure 9 with the upgrading process implemented in figure 8. In the comparative process of FIG. 9, the distillate residuum stream 85 is introduced into a hydrogen addition process 500. The hydrogen addition process 500 produces a hydrogenated heavy product 62 and a hydrogenated light product 64. The hydrogenated light products 64 can be introduced into a light distillate mixer 150 along with the distillate oil stream 80 to produce the mixed steam cracked feed 96. The mixed steam cracking feed 96 may be introduced to the steam cracking process 200. In both processes, an arabian medium crude oil with an API gravity of 31 and a total sulfur content of 2.4 wt% sulfur was used as crude oil feed 5.

The results are shown in Table 1.

TABLE 1 Properties of the streams

	Comparison (FIG. 9)	Upgrading process (figure 8)	Ratio of
				Crude oil feed flow (MT/day)	7062	7062	100％
Ethylene yield (MT/day)	973	1157	119％
				Propylene yield (MT/day)	524	603	115％
Fuel oil yield (MT/day)	3828	2696	70％

As can be seen from the results of table 1, the upgrading process described herein can produce more light olefins. For example, the upgrading process produced 19% more ethylene and 15% more propylene than the comparative process.

Although the present invention has been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention. The scope of the invention should, therefore, be determined by the following claims and their appropriate legal equivalents.

Unless otherwise specified, various elements described may be used in combination with all other elements described herein.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

Optional or optionally means that the subsequently described event or circumstance may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not.

Ranges may be expressed herein as from about one particular value to about another particular value, and include the endpoints unless otherwise specified. When such a range is expressed, it is to be understood that another embodiment is from the one particular value to the other particular value, and all combinations within the range.

Throughout this application, where patents or publications are referenced, the disclosures of these entire references are intended to be incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains, unless otherwise indicated herein by the conflict between such references and the statements made herein.

As used herein and in the appended claims, the words "comprise," "have," and "include," and all grammatical variations thereof, are intended to have an open, non-limiting meaning that does not exclude additional elements or steps, respectively.

Claims

1. A process for producing olefin gas from a cracked product effluent, said process comprising the steps of:

introducing the cracked product effluent into a fractionator unit configured to separate the cracked product effluent;

separating, in the fractionator, the cracked product effluent to produce a cracked light stream and a cracked residuum stream, wherein the cracked light stream comprises an olefin gas, wherein the olefin gas is selected from the group consisting of ethylene, propylene, butenes, and combinations thereof;

introducing the cracked residuum stream and a heavy feed into a heavy mixer;

mixing the cracked residuum stream and the heavy feed in the heavy mixer to produce a combined supercritical process feed;

introducing the combined supercritical process feed and water feed to a supercritical water process configured to upgrade the combined supercritical process feed; and

in the supercritical water process, the combined supercritical process feed is upgraded to produce Supercritical Water Process (SWP) -treated light products and SWP-treated heavy products, wherein the SWP-treated heavy products comprise a reduced amount of olefins and asphaltenes relative to the cracked residuum stream such that the SWP-treated heavy products exhibit increased stability relative to the cracked residuum stream.

2. The method of claim 1, further comprising the steps of:

introducing a crude oil feed and a hydrogen gas feed into a hydrogen addition process configured to promote hydrogenation of hydrocarbons in the crude oil feed, wherein the hydrogen addition process comprises a hydrogenation catalyst, wherein the hydrogenation catalyst is capable of catalyzing a hydrotreating reaction;

in the hydrogen addition process, subjecting hydrocarbons in the crude oil feed to the hydrotreating reaction to produce a hydrogenated stream, wherein the hydrogenated stream comprises paraffins, naphthenes, aromatics, light gases, and combinations thereof;

introducing the hydrogenated stream into a separator unit configured to separate the hydrogenated stream;

separating the hydrogenated stream in the separator unit to produce a light feed and a heavy feed, wherein the light feed comprises hydrocarbons boiling less than 650 ° F, wherein the heavy feed comprises hydrocarbons boiling greater than 650 ° F;

introducing the light feed and the SWP-treated light product into a light mixer;

mixing the light feed and the SWP treated light products in the light mixer to produce a combined steam cracked feed;

introducing the combined steam cracking feed to a steam cracking process configured to thermally crack the combined steam cracking feed in the presence of steam; and

in the steam cracking process, thermal cracking is caused to occur to produce the cracked product effluent.

3. The method according to claim 1 or 2, further comprising the steps of:

introducing the hydrogenated stream and the SWP-treated light product into a feed mixer;

mixing the light feed and the SWP-treated light product in the feed mixer to produce a combined separator feed;

introducing the combined separator feed into a separator unit configured to separate the combined separator feed;

separating the combined separator feed in the separator unit to produce a light feed and a heavy feed, wherein the light feed comprises hydrocarbons boiling less than 650 ° F, wherein the heavy feed comprises hydrocarbons boiling greater than 650 ° F;

introducing the light feed to a steam cracking process configured to thermally crack the light feed in the presence of steam; and

4. The method of claim 3, further comprising the steps of:

separating, in the fractionator unit, light gases from the cracked product effluent to produce a recovered hydrogen stream, wherein the recovered hydrogen stream comprises hydrogen; and

introducing the recovered hydrogen stream into the heavy mixer such that the combined supercritical water feed comprises hydrogen.

5. The method of claim 2, wherein the crude oil feed has an API gravity between 15 and 50, wherein the atmospheric fraction of the crude oil feed is between 10 and 60 vol%, wherein the vacuum fraction is between 1 and 35 vol%, wherein the asphaltene fraction is between 0.1 and 15 wt%, and wherein the total sulfur content is between 2.5 and 26 vol%.

6. The process of claim 2, wherein the hydrogenation catalyst comprises a transition metal sulfide supported on an oxide support, wherein the transition metal sulfide is selected from the group consisting of cobalt molybdenum sulfide (CoMoS), nickel molybdenum sulfide (NiMoS), nickel tungsten sulfide (NiWS), and combinations thereof.

7. The method of claim 2, wherein the hydrotreating reaction is selected from the group consisting of a hydrogenation reaction, a hydro-dissociation reaction, a hydrocracking reaction, an isomerization reaction, an alkylation reaction, an upgrading reaction, and combinations thereof.

8. A process according to claim 1 or 2 wherein the cracked resid stream comprises hydrocarbons boiling above 200 ℃.

9. A process for producing olefin gas from a cracked product effluent, said process comprising the steps of:

introducing the cracked residue stream and a distillate residue stream into a heavy mixer;

mixing the cracked resid stream and the distillate resid stream in the heavy mixer to produce a combined resid stream;

introducing the combined resid stream and a water feed to a supercritical water process configured to upgrade the combined resid stream; and

in the supercritical water process, the combined resid stream is upgraded to produce Supercritical Water Process (SWP) -treated light products and SWP-treated heavy products, wherein SWP-treated heavy products comprise a reduced amount of olefins and asphaltenes relative to the cracked resid stream such that SWP-treated heavy products exhibit increased stability relative to the cracked resid stream.

10. The method of claim 9, further comprising the steps of:

introducing a crude oil feed to a distillation unit configured to separate the crude oil feed;

separating the crude oil feed in the distillation unit to produce a distillate oil stream and a distillate residuum stream, wherein the distillate oil stream comprises hydrocarbons boiling at less than 650 ° F;

introducing the distillate oil stream to a hydro-addition process configured to promote hydrogenation of hydrocarbons in the distillate oil stream, wherein the hydro-addition process comprises a hydrogenation catalyst, wherein the hydrogenation catalyst is capable of catalyzing a hydrotreating reaction;

in the hydrogen addition process, subjecting hydrocarbons in the distillate oil stream to the hydrotreating reaction to produce a hydrotreated stream, wherein the hydrotreated stream comprises paraffins, naphthenes, aromatics, light gases, and combinations thereof;

mixing the hydrogenated stream with the SWP-treated light products in the feed mixer to produce a combined separator feed;

introducing the combined separator feed to a steam cracking process configured to thermally crack the combined separator feed in the presence of steam; and

11. The method according to claim 9 or 10, further comprising the step of

introducing the distillate oil stream and the SWP-treated light products into a distillate mixer;

mixing, in the distillate mixer, the distillate oil stream and the SWP-treated light products to produce a combined distillate oil stream;

introducing the combined distillate oil stream to a hydro-addition process configured to promote hydrogenation of hydrocarbons in the combined distillate oil stream, wherein the hydro-addition process comprises a hydrogenation catalyst, wherein the hydrogenation catalyst is capable of catalyzing a hydrotreating reaction;

in the hydrogen addition process, subjecting hydrocarbons in the combined distillate oil stream to the hydrotreating reaction to produce a hydrotreated stream, wherein the hydrotreated stream comprises paraffins, naphthenes, aromatics, light gases, and combinations thereof;

introducing the hydrogenated stream into a steam cracking process configured to thermally crack the hydrogenated stream in the presence of steam; and

12. The method of claim 10, wherein the crude oil feed has an API gravity between 15 and 50, wherein the atmospheric fraction of the crude oil feed is between 10 vol% and 60 vol%, wherein the vacuum fraction is between 1 vol% and 35 vol%, wherein the asphaltene fraction is between 0.1 wt% and 15 wt%, and wherein the total sulfur content is between 2.5 vol% and 26 vol%.

13. The process of claim 10, wherein the hydrogenation catalyst comprises a transition metal sulfide supported on an oxide support, wherein the transition metal sulfide is selected from the group consisting of cobalt molybdenum sulfide (CoMoS), nickel molybdenum sulfide (NiMoS), nickel tungsten sulfide (NiWS), and combinations thereof.

14. The method of claim 10, wherein the hydrotreating reaction is selected from the group consisting of a hydrogenation reaction, a hydro-dissociation reaction, a hydrocracking reaction, an isomerization reaction, an alkylation reaction, an upgrading reaction, and combinations thereof.

15. The process of any of claims 9 to 14 wherein the cracked resid stream comprises hydrocarbons boiling above 200 ℃.

16. A process for producing olefin gas from a cracked product effluent, said process comprising the steps of:

introducing the cracked residuum stream and a hydrogenation stream into a heavy mixer;

mixing the cracked residuum stream and the hydrogenated stream in the heavy mixer to produce a mixed stream;

introducing the mixed stream and a water feed to a supercritical water process configured to upgrade the mixed stream; and

in the supercritical water process, the mixed stream is upgraded to produce Supercritical Water Process (SWP) -treated light products and SWP-treated heavy products, wherein the SWP-treated heavy products comprise a reduced amount of olefins and asphaltenes relative to the cracked residuum stream such that the SWP-treated heavy products exhibit increased stability relative to the cracked residuum stream.

17. The method of claim 16, further comprising the steps of:

introducing the combined distillate oil stream into a steam cracking process configured to thermally crack the combined distillate oil stream in the presence of steam;

in the steam cracking process, causing thermal cracking to occur to produce the cracked product effluent;

introducing the distillate raffinate stream to a hydro-addition process configured to promote hydrogenation of hydrocarbons in the distillate raffinate stream, wherein the hydro-addition process comprises a hydrogenation catalyst, wherein the hydrogenation catalyst is capable of catalyzing a hydrotreating reaction; and

in the hydrogen addition process, hydrocarbons in the fraction residuum stream are subjected to the hydrotreating reaction to produce the hydrogenated stream, wherein the hydrogenated stream comprises paraffins, naphthenes, aromatics, light gases, and combinations thereof.

18. The method of claim 16 or 17, wherein the crude oil feed has an API gravity between 15 and 50, wherein the atmospheric fraction of the crude oil feed is between 10 and 60 vol%, wherein the vacuum fraction is between 1 and 35 vol%, wherein the asphaltene fraction is between 0.1 and 15 wt%, and wherein the total sulfur content is between 2.5 and 26 vol%.

19. The process of claim 17, wherein the hydrogenation catalyst comprises a transition metal sulfide supported on an oxide support, wherein the transition metal sulfide is selected from the group consisting of cobalt molybdenum sulfide (CoMoS), nickel molybdenum sulfide (NiMoS), nickel tungsten sulfide (NiWS), and combinations thereof.

20. The method of claim 17, wherein the hydrotreating reaction is selected from the group consisting of a hydrogenation reaction, a hydro-dissociation reaction, a hydrocracking reaction, an isomerization reaction, an alkylation reaction, an upgrading reaction, and combinations thereof.

21. A process according to any one of claims 16 to 20 wherein the cracked resid stream comprises hydrocarbons boiling above 200 ℃.